dc.creator Peterson, K. A. en_US dc.creator Werner, H.- J. en_US dc.date.accessioned 2006-06-15T18:51:16Z dc.date.available 2006-06-15T18:51:16Z dc.date.issued 1993 en_US dc.identifier 1993-RC-10 en_US dc.identifier.uri http://hdl.handle.net/1811/18518 dc.description Author Institution: Molecular Science Research Center, Pacific Northwest $Laboratory^{\dag}$.; Fakult\""{a}t f\""{u}r Chemie, Universit\""{a}t Bielefeld en_US dc.description.abstract The photodissociation mechanism of the $ClO_{2}$ radical which gives rise to chlorine atoms has been investigated using large scale internally contracted multireference configuration interaction wave functions. Potential energy surfaces of the OClO isomer have been calculated for the process: $OClO (X^{2}B_{1}, ^{2}B_{2}, ^{2}A_{1}, A^{2}A_{2}) \to, Cl (^{2}P) + O_{2} (X^{3} \Sigma_{g}{^{\,-}},a^{1} \Delta_{g})$ The lowest energy pathway is calculated to occur via the $^{2}B_{2}(^{2}A)$ potential energy surface with a barrier of less than I eV. The structure of the transition state is only slightly distorted from $C_{2v}$ symmetry, which is in excellent agreement with the recent experiments of Davis and $Lee.^{1}$ Competition between this chlorine-producing channel and the dominant one, $OClO to ClO (X^{2}\Pi) + O (^{3}P)$, results in the strong vibrational mode specificity also observed experimentally. Additionally, these calculations indicate that the branching ratio for production of $X^{3} \Sigma_{g}{^{\,-}}$ and $a^{1}\Delta_{g}O_{2}$ is dictated by the intersection of the $^{2}B_{2}$ and $^{2}A_{1}$ surfaces, which occurs at geometries close to the transition state. $^{1}$ H.F. Davis and Y.T. Lee. J. Phys. Chem. 96, 5681 (1992). en_US dc.format.extent 91526 bytes dc.format.mimetype image/jpeg dc.language.iso English en_US dc.publisher Ohio State University en_US dc.title THE PHOTODISSOCIATION OF OClO: PATHWAYS OF CHLORINE ATOM PRODUCTION. en_US dc.type article en_US
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